Concrete and stucco paint oil.



UNITED STATES PATENT OFFICE.

GARLETON ELLIS, MONTCLAIR, NEW J EBSEY, ASSIGNOE TO ELLIS-FOSTER COMPANY A CORPORATION OF NEW JERSEY.

CONCRETE AND STUCCO PAINT OIL No'Drawing. v

Specification of Letters Patent.

Application filed May 20, 1911.

To all whom it may concern.

Be it known that I, CARLETON ELLIS, a citizen of the United States, residing at Montclair, in the county of Essex and State of New Jersey, have invented certain new and useful Improvements in- Concrete and Stucco Paint Oil, of which 'the following is a specification.

This invention relates to concrete oils, and particularly to oils containing metallic soap, which have desirable colloidal or body- .ing qualities and resistance to saponification.

In a patent application, entitled, Binding and coating compositions, Serial No. 552,178,'filed March 29th, 1910, and in a patent application, entitled, Coated concrete Serial No. 588,549, filed Oct. 22nd, 1910, and

in a patent application, entitled, Waterproof coating for concrete, eta, Serial No. 608,888, filed Feby. 16th, 1911, I have set forth the advantages derived from the use of unsa nifiable resins, such as Jellutong, or Pontianac resin. .The present invention has to do in part with the utilization of substantially water insoluble metallic soaps and particularly the aluminum zinc iron and calcium or magnesium soaps of fatty acids, in particular those produced by combination with a drying oil, as colloidal thickness in concrete oil compositions. I

The presence in concrete of a considerable amount of alkali makes it undesirable to use saponifiable oils, such as linseed oil as a base for-.concrete paint. An unsaponifiable or alkali resisting coating is required and. this can be secured advantageously only by the use of an unsaponifiable resin, or by the use of a saponifiable body which has been so treated that it does not readily sap'onify. A product of the latter character is securedbysapo'ni ing a drying oil, such as linseed oil, fish, hinese wood oil, corn "or cotton seed 'oil with caustic alkali and subsequently precipitating the soap formed in this manner by a soluble salt of aluminum, or any other suitable metallic salt which forms asubstantially water insoluble soap. Inasmuch as lime is the active ingretageoiisly used'.' Theiluminumsoapshowclient, to a very' large extent, in concrete, the lime soaps of these oils may be advanever, have great bodying properties andare to be preferred when a viscous Oil is desired.

. stances.

bonated andis not as active.

Concrete is a very porous material as ordinarlly prepared and absorbs oils very easily by capillary action. This action is known in the trade as suction and oils are frequently required which resist the suction of the concrete. For such purposes the aluminum soaps, because of their great colloiding or bodying properties and resistance to saponification, are highly desirable additions to the concrete oils. In themselves, they may even be used in simple solution, or with the addition of a small amount of drier for certain applications. However, I prefer to make use of such insoluble soap compounds .in conjunction with an insoluble resin, such as Pontianac or -J ellutong resin, as by combining these two materials, or their equivalents, concrete oils are secured which are resistant to saponification, which have the necessary body to resist suction and which have a substantial quantity of Water resistant material, so that water proofing efiects maybe obtained by the application of not more than one or two coats.

While, as stated, I make use of metallic soaps of various oils, I prefer to use those derived from the drying oils and in particularlfrom fish oil or Chinese wood oil.

Preferably, I also employ the aluminum soaps of these oils. Under some conditions of mixing, these metallic soaps have a fiatt-ing action. That is to say, they convert a resin solution or varnish composltion which dries glossy into a dull surfaced material; a feature which is called for occasionally.

The manner in which I prefer to produce the soaps above referred to is that of saponitying by boiling the oil with an alkali and subsequently precipitating the metal soap as above indicated, but I may make use of other methods of producing this material, as, for example, by heating the-oils with the 'oxids of metals, so as toproduce oil soluble compounds. The oil may be treated so as to be completely saponified by the use of the caustic alkali, and so as to form, by precipitation, a metallic soap in which, consequently, all the oil is converted into a soap, or it may be partially saponified according to circum- If concrete is not aint'ed until it has been exposed to the weat er for a number of years,which is sometimes the case, a good .deal of the alkali has become car Under such circumstances, the presence of a moderate amount of saponifiable oil, especially if accompanied by a large proportion of unsaponifiable' material, is not always objectionable.

A partially saponified composition may be made by mixing 1 qt. of wood oil, 1 qt. of water; and.3% fi. oz. of caustic soda of 50% strength. This is boiled for about an hour or until saponification has absorbed the alkali. After saponification is completedlb. of pulverized Pontianac resin may be added to the solution. 6 oz. of concentrated alum are dissolved in gal. of hot water. This is added gradually to the wood oil soap to completely throw down the oil mixture. The composition is washed two or three times with water-and then as much water as possible removed from the material by slight pressure or draining and the product is then placed in a kettle and heated to expel the remainder of the moisture. 3% lbs. of the Pontianac resin are melted and thinned with 1 gal. of benzol. 1 to 2 lbs. of the saponified wood oil compound are dissolved in a gal. of the Pontianac resin solution. This may be accomplished by having the wood oil compound a melted condition and adding the Pontianac resin solution gradually. 3% to 5% of wax may be added if it is desired to increase the flatting action. The Pontianac resin may, if desired, be heated to 500 or 600 degrees F. for an hour or more before thinning with the benzol, or other solvent, in which case higher concentration of the resin is made possible, as it becomes more soluble in hydrocarbon solvents after being so heated, The aluminum compound prepared in this way increases the body of the oil and may be used in larger proportion if greater body is desired. 3 lbs. of the Pontianac resin either heat treated, or untreated, and 3 lbs. of the aluminum compound to a gallon of benzol give a composition of a high body. When a compound is required which is completely saponified, the proportions may be 1 qt. of the wood oil, 2 qts. of water, and 6 oz. of dry caustic soda, which mixture is boiled for one-half hour or more, until the oil is completely saponified. 1 lb. of the powdered Pontianac resin is then added and the mixture boiled five minutes longer. 1 lb. of concentrated alum is dissolved in i to gal. of hot water and added to the soap material. The composition is washed and dried. This forms a very tough mass, which is difiicult to melt, and to assist in the melting, Pontianac resin may be melted with it, or a larger proportion of the Pontianac resin, or other resin or flux added to the wood oil soap at the time of precipitation. From this material a concrete oil may melting one lb. of the. aluminum tungate with 2 lbs. of Pontianac resin, thinning with 5% lbs. of benzol and adding lb. of Japan be made by,

drier. A still heavier bodied compound made by using 2 lbs. of the aluminum tungate in place of the 1 lb. indicated in the above formula. This composition contains not wood oil therefore, but the products of the reaction of the aluminum salt on the sodium soap of the wood oil. Wood oil is a glycerid and on treatment with the caustic soda the wood oil is decomposed into a sodium soap, containing sodium oleomargarate; and the glycerin which is separated from the oil goes into solution in the water. On the addition of the aluminum solution or similar precipitating agent, a metallic soap is formed from these fatty acids which is entirely different from the wood oil chemically and physically, and is, in fact, an entirely different body. The aluminum tungate also differs from the wood oil in respect a of Pontianac resin, or ordinary rosin. 12

oz. of concentrated aluminum are dissolved in gal. or so of hot water and used to precipitate the soap or fish oil to form the aluminum compound. This is washed and dried. 1 part of this compound and 1% parts of J ellutong resin may be dissolved in four parts or so of benzol and a small amount of drier added. Another formula is prepared by dissolving 2 lbs. of the aluminum fish oil compound in 4 lbs. of benzol or petroleum naphtha, adding of an ounce of Japan drier. Still another compound which is useful as a concrete oil, may be made by mixing equal parts of this benzol solution and a benzol solution containing 3% lbs. of Pontianac resin to the gallon of the benzol.

Although aluminum soap alone may be used by itself in a suitable hydrocarbon solvent, it is undesirable to use it in this way ordinarily, because the very property which makes it possible to secure a high degree of body in the oil, limits the amount which may be put into solution and while body is secured there is not sufiicient non-volatile material in the oil for properly waterproofing concrete exposed to severe service conditions, except by the application of anumber of coats. Therefore the combination of the Pontianac resin, or other unsaponifiable resin, which does not give a high body to the oil, makes it possible to secure both body and substance in a composition which has the requisite degree of unsaponifiability, resistance to moisture and waterproofing qualities in general, and durability.

' a fluxing material, is not ordinarily desirare not very durable. used to some slight extent as a fluxing agent,

able, as the water insoluble soaps of rosin It may however, be

and the resinate f aluminum'may be used 7 more or less, especiallyif the concrete to be treated does not rece1ve very severe exposure. The aluminum soap of fish oil and aluminum tungate are however by far the most satisfactory and are therefore used in my invention in its preferred embodiment.

It should be understood that I may vary the proportions of the materials used in the above illustrative formulas, to secure soaps completely o partially saponified, although in general, as I have stated, I prefer to completely saponify the oil so as to produce a water insoluble metallic compound, soluble in oil or hydrocarbon solvent, which is substantially free from unsaponifiable matter, the latter term being used in the sense that the metallic com pound is free from material which would be affected or saponified by the alkali of concrete. It should be added that aluminum or other soaps of stearic palmitic and oleic acids and the like have been prepared heretofore and made up into'the form of solutions. I have observed a certain degree of instability in certain of these compounds, as for example, pure aluminum palinitate dissolved in turpentine forms first a compound of considerable body, but on standing for a year or more, the solution becomes thin and possessed of but little viscosity. The degree of permanency as secured by the combination of an aluminum base with raw fish oil or wood oil as aboveindicated secures compounds of much greater stability.

To secure various degrees of drying, small amounts of driers, such as lead linoleate, or oleate, manganese resinate, or other metallic soaps soluble-in oil, having drying properties, say from 1% to 2%, or thereabout, may be introduced, but the addition of such strong driers, in large quantities is objectionable, as they'tend to make the dried: film highly brittle in the course of time.

The present invention also involves the process of coating concrete consisting in applying these liquid mixtures to the concrete either by means of a brush or by spraying with suitable spraying device. The latter method is more satisfactory than applying by means of a brush, as cement and stucco is often characterized by a very rough surface finish and the material does not penetrate as well when applied by brush as when forcibly impinged on the walls by means of a sprayer. Commonly the oil carries a pigment which should be of a nature fast to lime. This excludes colors such as Pru s- I sian blue and the like, which are affected by alkalis. It should be further noted that I do not wish to limit myself to the precise-ingredients or proportions indicated in this illustrative Way, but may invoke the doctrine of equivalency in so far as the same may be herein applicable.

In Serial No. 588,549, I have set forth the method of waterproofing concrete, consisting in applying to the surface of such concrete a resin or resinous-body, of a sub-- stantially unsaponifiable character and in the present invention I have set forth the I use of resinous bodies which are saponifiable in their natural state, but whose ability to saponify has been greatly reduced, or substantially eliminated by combination with lime, alumina or other basic materials, with. the object of forming a substantially water insoluble metallic soap of a resinous body which would dissolve readily in hydrocarbon solvents such as benzol and benzin and I have also set forth compositions containing entirely unsaponifiable bodies or bodies which are naturally unsaponifiable with resinous bodies which have been treated so as to make them substantially immune to the action of the alkali of the Portland cement and the present invention contemplates also the process of applying such neutralized resinous bodies in suitable solution to concrete for the purpose of waterproofing it and it also comprises the process 'of Waterproofing concrete, which involves superficially impregnating and coating the exposed surface of concrete, with a medium comprising an unsaponifiable or alkaliproof or resinous body, con-- taining a lime soap, all dissolved in a suitable solvent and furthermore the similar treatment with mixtures of such lime soapsand unsaponifiable resin ora resin such as Pontianac which is substantially unsaponifiable.

As set forth above, the principal active alkali of the concrete is lime, and the formation of a limesoap of a fatty acid especially an acid having drying qualities, would at first sight apparently be a very satisfactory method of solving the problem of making a concrete oil. Unfortunately however, lime soaps are prone to undergo hydrolysis and therefore in the present invention, special stress is laid on the combination of such soaps with the substantially unsaponifiable resin or resinous body, or the incorporation of unsaponifiable material such as very heavy hydrocarbon oils or'waxes, such as ceresin and paraffin wax.

The following formulas illustrate various combinations of lime soap, solvents and the like:

l resin and kauri gum are melted together,

'2 parts of wood oil and a trace of lead oleate. V

Another formula consists of 4 parts of Pontianac resin, 2 parts of lime fish oil soap, 2 parts of lime wood oil soap, 8 parts of thinner and a trace of drier.

Another formula consists of kauri resin 4 parts, lime tungate 4 parts, thinner 12 parts, wood oil 2 parts, and a trace of drier.

Another formula consists of Pontianac resin 4 parts, lime tungate 2 parts, thinner 8 parts, ceresin Wax 1} part, and a trace of drier.

Another formula consists of Pontianac resin 4 parts, lime tungate 2 parts, wood oil 2 parts, thinner 8 parts and a trace of drier.

Another formula consists of Pontianac resin 3 parts, kauri resin 1 part, ceresin wax 1 part, the lime soap of fish oil 1 part, aluminum tungate 1 part, wood oil two parts and thinner 10 parts.

In connection with the preparation of lime tungate or aluminum tungate or other tungate soaps, it is to be noted that if these are heated to certain temperatures polymerization takes place resulting in prod-. ucts which have very marked thickening qualities. If, for example, lime tungate 2 parts, and Pontianac resin 2 parts, are heated to 210 degrees cent. which is practically the lowest temperature at which they can be melted together in a quick and satisfactory way, and this mixture is thinned with three parts each of benzin and benzol, a very heavy bodied liquid is secured. If however, the lime tungate has been heated to 260 degrees, C. or higher and thinned in the same way, a jelly, or solid is secured, which dissolves to a liquid only after warming an additional quantity of the thinner. This method affords a means ofincreasing the body of the concrete oil preparation for those cases where suction is very marked.

In Serial No. 588,549, allowed'May 11th, 1911, of which this application is a divisional continuation, that is, contains subject matter from said allowed application, and in Serial No. 608,888, I have called attention to the difficulty of securing solutions of unsaponifiable resinous bodies such as Pontianac resin in strength or concentration sufliciently great for practical commercial use as" water-proofing finish coatings for concrete. Unlike colophony and similar resins, Pontianac resin has not been re arded as readily soluble in hydrocarbon sofvents. In naphtha and similar solvents, the solubility has been given by Chute, (India Rubber W 01 M, July 1909) as 1:34,.that is,.tw,o parts of the resin requiring 7 parts of solvent or a saturated solution carrying about 20% of.

the resin. It is obvious that under such conditions of 'solubility a simple solution of the resin in a hydrocarbon solvent would have relatively so little solid material and so large a proportion of volatile material, (approximately 80%, all of which would be wasted) that such a solution would not be well adapted for filling the pores of and waterproofing concrete without the use of an excessive number of'coats. Then too, the instability of many of such solutions, (as I have set forth in Serial No. 608,888) militates against their indiscriminate use. By using coal tar naphtha composed of benzene or benzin and toluol, I have found a compatible volatile solvent capable of forming permanent solution in the ratio of about 1:2, that is, one part of the resin is fully dissolved in about two parts of such a compatible solvent. Thereby a solution is secured having about the same concentration of non-volatile matter as is obtained in the manufacture of many varnishes, etc., thus permitting of waterproofing of concrete by only one or two coats and effectively treating the concrete surface quickly and inexpensively. A simple formula consists in melting 1 part of Pontianac resin and thinning with about two parts of light coal tar naphtha. Another formula consists of 1 part of Pontianac resin, 2; part of ceresin wax, or montan wax and two parts of the naphtha. Another formula consists of 1 part Pontianac resin, part of spindle oil, part of wood oil and two parts of the naphtha. Still another formula consists of 1 part Pontianac resin, part of kauri gum, part each boiled wood oil and fish oil and 1 parts naphtha. Petroleum naphtha, in conjunction with coal tar naphtha may be used more or less, especially if, as set forth in Serial No. 588,549, the petroleum product is more volatile than the aromatic product. In

the foregoing formulas the coal tarnaphtha may be replaced to the extent of from 10% to 20%, more or less, by petroleum naphtha.

\Vhat I claim is 1. A concrete paint, comprising a waterinsoluble soap of a fatty acid, an unsaponifiable resinous body and a hydrocarbon solvent, said composition being fluent and flowable and of about the consistency of linseed oil'.

2. A concrete paint oil, comprising the aluminum soap of a fatty acid, an unsaponifiable resinous body and a hydrocarbon solvent, said composition being fluent and flowable.

3. A concrete paint oil comprising the aluminum soap of a drying oil and an urisaponifiable resin all in solution in a suit-' able solvent.

4. A concrete paint oil comprising the aluminum soap of a drying oil, Jellutong resin and a hydrocarbon solvent.

5. A concrete aint oil, comprising the aluminum soap 0 wood oil, Pontianac resin and a hydrocarbon solvent.

6. A concrete paint oil comprising aluminum tungate and Pontianac rubber resin in about equal proportions in solution in a solvent comprising benzol.

7 A concrete paint oil, comprisin a solution containing about equal parts 0 aluminum tungate and Pontianac resin and a modicum of a drier.

8. A concrete paint oil, comprising an oil soluble soap of tung oil, an unsaponifiwood'oil and a hydrocarbon able resin, Wax, solvent.

'9. A composition for coating concrete comprising a substantially unsaponifiable resinous body, a bodying material and a thinner.

10. A composition for coating concrete comprising essentially a substantially unsaponifiable resinous body, a solvent therefor and an alkali-resistant colloid thickener.

11. A composition for coating concrete comprising essentially a substantially unsaponifiable resinous body, a solvent therefor and a colloid thickener. V

In testimony whereof I have afiixed my signature in presence of two Witnesses.

GARLETON ELLIS. Witnesses BIRDELLA M. ELLIS, SYDNEY M. SrEDoN. 

